DE1179768B - Liquid or liquid-viscous to solid fuel for liquid or solid rocket and / or nozzle propellants - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: F 02 k

Number: File number: Registration date: Display day:

German class: 46 g -20

B 58985 VIb / 46 g
August 16, 1960
October 15, 1964

The invention relates to isomer mixtures of saturated polycyclic hydrocarbons with bridge bonds, which are suitable for numerous purposes, but especially as very high-energy Fuels, e.g. B. for jet engines, turbine nozzles, rockets, projectiles and other engines can. The invention further relates to methods of making these isomer mixtures as well on the substances occurring as intermediate products and the processes for their production.

Further possible uses of the mixtures prepared according to the invention, insofar as they have a lower Have viscosity grade, are used as hydraulic fluids, transformer oils and as heat transfer fluids. So much for the mixtures prepared according to the invention have a higher viscosity or are polymeric forms, they can be used as lubricants of high stability or as a plasticizer and extender for elastic and plastic materials.

The hydrocarbon mixtures according to the invention having a number of 14 to 30 carbon atoms are liquid over a wide temperature range. They have relatively high boiling points and relatively low ones Freezing points. They also have a high energy content, i. H. a high number of calories, based on the volume unit, and are characterized by a relatively high density. This combination of These properties make them particularly suitable for use as fuel for jet engines.

The mixtures which can be used according to the invention as fuels for jet engines consist of Positional isomers of the di- (lower alkylcyclohexyl) alkanes and the (lower alkylcyclohexyl) - (cyclohexyl) alkanes the formula below

where R ¹ and R ^{2 are} unbranched or branched, lower alkyl radicals with 1 to 13, preferably 1 to 5 carbon atoms, Y is a straight or branched alkylene radical with 1 to 13 carbon atoms which serves as a bridge, m is an integer from 1 to 3, η is a integer from 1 to 4 and

means a saturated benzene nucleus (cyclohexyl).

More liquid or more viscous to solid
Fuel for liquid or solid rocket
and / or jet fuels

Applicant:

Dr. phil. Oliver Wallis Burke jun.,
Pompano Beach, Fla. (V. St. A.)

Representative:

Dipl.-Chem. Dr. rer. nat. H. Kainer,

Patent attorney, Heidelberg, Steubenstr. 22-24

Named as inventor:

Dr. Eldon Everett Stahly, Birmingham, Mich.

(V. St. A.)

Claimed priority:

V. St. v. America 17 August 1959

(833 996)

The total carbon number, when the compounds are liquid, is between 14 and about 30 carbon atoms. With a higher carbon number, the compounds represent mixtures of viscous-liquid until solid.

The specific gravity of the liquid mixtures is generally above 0.8. Under "high density" Therefore, liquids are understood here that have a density of 0.8 or more. The in kcal The measured heat of combustion of the mixtures is usually above 8.323 kcal, based on 11. Below An "energy-rich fuel" is therefore to be understood in the following to mean a combustible mixture that has at least the stated kcal value. For example, the density is that of the invention Jet engine fuels usually in the range of 0.85 to about 0.91 and the kcal in the range of about 8.788 to about 9.321 kcal / l.

In the formulas given here, the lower alkyl radicals R ¹ and R ² include the C ₁ - to C ₁₃ -alkyl radicals, such as methyl, ethyl, propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, n-amyl , the isoamyls, tert-amyl, n-hexyl, the isohexyls, tert-hexyl, diisopropyl, n-heptyl, isoheptyl, diisobutyl, 2-ethylhexyl, triisopropyl, n-nonyl, n-dodecyl, tetraisopropyl, triisobutyl, tridecyl and other isomers thereof. R ¹ and R ² can represent the same or different alkyl radicals.

409 707/111

In the formulas I to IX, all divalent, acyclic radicals can be used as the bridge-forming alkylene radicals Hydrocarbon radicals with a carbon number of 1 to 13 are used, which form the two ring-shaped Hydrocarbon radicals on the same carbon atom or on different carbon atoms the bridge Y connect. The alkylidene bridge Y is therefore a special case of the alkylene bridge Y.

In the formulas for hydrocarbons listed here, the bridge
adhere to one of the following radicals:

Methylene (-CH ₂ -),
Ethylidene (= CHCH ₃ ),
Ethylene (- CH ₂ CH ₂ -),
n-Propylidene-1,1 (= CHCH ₂ CH ₃ ).

Propylidene-2.2 CH ₃ CCH ₅

Propylene-1,2 I-CH ₂ CHCH ₃ / propylene-1,3 (- CH ₂ CH ₂ CH ₂ -), n -butylidene-1,1 (= CHCH ₂ CH ₂ CH ₃ ). Isobutylidene-1,1 (= CHCH [CH ₃ J ₂ ), η = 2 , the number of isomers increases to six and, with m = 2 and η = 3, even to at least thirty-six isomers. Where isomerism can be due to the different arrangement of the rings on the alkylene bridge Y, the number of isomers is considerably greater. The number of isomers increases further with the number and the isomerism possibilities of the alkyls. In addition, as will be shown below, some of the cyclic radicals

Y, for example, from io kale from hydrocarbon fractions, which consist of many

component mixtures of alkyl-substituted aromatic hydrocarbons from which the end products are obtained. This results in mixtures of even greater complexity. The fuels according to the invention therefore consist of mixtures of a large number of positional isomers and of homologues which arise in the processes described below. The fact that the fuels consist of mixtures is therefore particularly desirable because a mixture enables the production of e.g. B. a rocket fuel, which is usually liquid with a carbon content of 14 to 30 carbon atoms, has a fairly high boiling point, a relatively constant high density and at low temperatures has a low viscosity. The mixtures according to the invention also have very low freezing points, which are often 50 ^° C. below those of the pure isomers.

Another advantage of the fuels according to the invention is that they, regardless of the fact that they consist of mixtures, made exactly according to the requirements desired for rocket propellants can be, whereby for the production process are used which as such are extraordinary are economical.

As mentioned earlier, the total number of carbon atoms when the mixtures are considered to be at room temperature Liquid fuels should be used in the range between 14 and about 30 carbon atoms. Within this range, the number and number of alkyl and alkylene substituents Chain length can be chosen arbitrarily. For example, the length of the carbon chain of the alkylene bridge are reduced to a carbon number of preferably 1 to 5 carbon atoms, while at the same time the number and the carbon number of the alkyl groups substituted on the ring is increased and vice versa.

Outside the stated limits, the isomer mixtures according to the invention constitute viscous oils or solid substances. These can also be used as fuels. However, if they are considered liquid If fuels are to be used, they must be heated or even melted to reduce their viscosity will.

The choice of a range between 14 and about 30 carbon atoms in the liquid fuels according to the invention and the measure of producing a large number of positional isomers has the advantage that the mixtures are usually uniform with regard to the number of carbon atoms or with regard to a specific application In this respect, mixtures of numerous positional isomers can be made relatively uniform. For example, as described below in e.g. B., in the simplest case, when R = methyl, numerous examples are shown, each product Y = methylene, m = 1 and η = 1, to be expected at least from a mixture of compounds with the same three positional isomers. If m = \ and number of carbon atoms exist. If the

CH ₃
Isobutylene -1,31- CH ₂ CHCH ₂

n -Butylidene-2.21 CH ₃ CCH ₂ CH

n-Butylene-1,2 (- CH ₂ CHCH ₂ CH ₃ J, n-Butylene-1,3 (- CH ₂ CH ₂ CHCH ₃ ), n-Butylene-1,4 (- CH ₂ CH ₂ CH ₂ CH ₂ -), isobutylene -1.2 (-CH ₂ C [CH ₃ ] J,

J.

n-butylene-2,3 (CH ₃ CHCHCH ₃ J, n-pentylidene-1,1 (= CH [CH ₂ J ₃ CH ₃ ),

/ CH ₃

Isopentylene-1,4 \ - CH ₂ - CHCH ₂ CH ₂ - n-PentyIen-1,2 (- CH ₂ CH- [CH ₂ J ₂ CH ₃ / n-hexylidene, n-hexylene-1,2, n- 1,3-hexylene, 1,4-hexylene, 1,5-hexylene, 1,6-n-hexylene, isohexylidene, 1,2-isohexylene, n-heptylidene, 1,7-isooctylene, n- Nonylidene, n-decylidene, n-undecylidene, n-dodecylidene and n-tridecylidene,

including the various isomers and homologues having no more than 13 carbon atoms.

Make the compounds prepared by the methods described in detail below

Ring substituents originate from a commercially available mixture of C ₇ - to C ₉ aromatics, the total carbon number of the various compounds of the mixture obtained varies only within a narrow range. Of course, side reactions such as B. a further condensation, compounds with a higher number of carbon atoms, such as. B. tri- or polycyclic alkanes, e.g. B. di- (alkylcyclohexylmethyl) -alkylcyclohexanes, di- (alkylcyclohexylethyl) -alkylcyclohexanes and the like. However, these polymeric compounds with numerous bridges and rings, since they have higher boiling points, can easily be separated off in the distillation. Where a wide boiling range fuel can be used and the end products are highly viscous liquids or solids, the higher condensation products need not be removed. The higher condensation products can be illustrated by the following formulas:

The mixture of isomeric compounds of the formulas V, IV and VI which occurs as an intermediate is preferably made by reacting a bridging agent with an alkylbenzene or a mixture of various alkylbenzenes, whereby benzene can be used instead of one of the alkylbenzenes, manufactured.

Another, but less economical, way is to first use a di- (phenyl) -alkylene formula

Y-

VII

(R ¹ V ^: Hj-

-Y-I-H

II

-H-

Y-

X /

(R ² V ₁

III

Here, ρ denotes an integer with the value 2 or 3, while R ¹ , R ² , Y, m and η have the same meaning as in formula I.

The compounds illustrated by Formula I are usually prepared by hydrogenation of an as Intermediate di- (alkylphenyl) alkane or (phenyl) - (alkylphenyl) alkane of the following Formula made:

where Y has the same meaning as in the formulas I and IV, by means of the bridging reactions also used in the compounds of the formula IV, and the compound of the formula VII thus obtained then using conventional alkylation methods with substitution with one or more alkyl groups R ¹ or R ^{2 of} the formula or a mixture of both to alkylate on the rings. This results in mixtures of the isomers of the formula IV used as intermediates.

Another method for preparing a mixture of compounds of Formula VII is in linking the phenyl groups with the bridging agent and at the same time one or both rings with one or lower lower alkyl groups in The presence of a catalyst to alkylate both the alkylation and the bridging reaction catalyzed in the same reaction mixture.

The bridging reactions preferably used include the alkylation of two phenyl groups, at least one of which is selected from an alkylphenyl group the formula

(R ¹ ),

IV

Here, R ¹ , R ² , m and η have the same meaning as in formula I. Y can consist of any acyclic carbon radical having 1 to 13, preferably 1 to 5, carbon atoms.

The compounds illustrated by Formula II and III are prepared by hydrogenation of an intermediate of the formulas below:

(R ¹ VI -J

y \

-Y

-Y-

(R ² V ₁

VI

Here, R ¹ , R ² , Y, p, m and η have the same meaning as in formula III.

in which the symbols have the meaning given above, consists with a single alkane, such as. B.

Acetylene, a diene hydrocarbon, an aliphatic containing oxygen or 2 halogen atoms Connection. Here, in the presence of an alkylation catalyst, e.g. B. an acid catalyst, usually a strong mineral acid such as sulfuric acid, phosphoric acid and / or hydrofluoric acid, or a connection, such as B. a boron halide or their complex compounds, such as. B. boron trifluorite phenylate, Boron trifluoride etherate, boron triflubride, dissolved in sulfuric acid or other acidic alkylation and condensing agents with or without Friedel-Crafts type catalysts. If the bridging agent has two halogen atoms, a Friedel-Crafts catalyst such as z. Aluminum chloride, can be used alone.

When sulfuric acid is used as catalyst, its concentration is usually higher than 80 ° / _0, but may generally below about 98% "because when using higher concentrated sulfuric acid enter sulfonation of the aromatic rings or excessive formation of polycyclic compounds.

In particular, those catalysts are used which one of aliphatic compounds, such as

ζ. B. aldehydes, glycols, alkylene oxides, acetylenes, Diene hydrocarbons and in particular conjugated diene hydrocarbons and dihaloalkanes, introduce derived bridging group. Acetylene itself and higher alkynes can also be used as Bridging agents are used. When using acetylene and other alkynes as bridging agents the catalyst usually consists of mercury sulfate, which is mixed with a strong acid, such as. B. 85 to

Refining reformate, which contains an economically workable amount of aromatic hydrocarbons, is a valuable starting material from which an aromatic extract can be obtained which can serve as a source of the alkylbenzenes either as such or in the form of its individual fractions. A typical C ₈ fraction used contains e.g. B. about 2% toluene, 10% p-xylene, 48% m-xylene, 19% o-xylene and about 21%

sculptor, applied. The catalyst is usually added at room temperature. If the bridge builder is difficult to make to react,

the work is carried out at low temperatures and the bridging agent is usually slow, e.g. B. drop by drop in the course of several, usually 4 to 12 hours

98% sulfuric acid or a boron trifluoride io ethylbenzene. Phosphoric acid complex, is activated. The alkyl- When the bridging reaction is carried out,

tion reactions are obtained in a manner known per se in the if predominantly the bicyclic compound generally at room temperature and sometimes it should be, the alkylbenzene is usually considerably lower Temperatures such as B. between 0 and Lichem excess, ζ. B. in a 2 to 3 fold ± 30 ° C. Some catalysts, such as a 15 molar excess based on the molar amount z. B. hydrofluoric acid, can be applied to a considerable amount of the bridging agent. If against it temperatures below room temperature, higher polycyclic compounds, such as. B. the tribe for example - 20 ° C or below, uses cyclic or polycyclic compounds of the will. Formulas II, III, V and VI are to be obtained,

Typical for the preparation of alkylphenyl groups 20 is reduced to a lower ratio serving to about ₂ V substances are: toluene, o-, m ~ or up to 3 mole of alkylbenzene, based on 1 mol Brückenp-xylenes, and mixtures thereof, the trimethylbenzenes,
such as B. mesitylene, ethylbenzene, diethyl and
Triethylbenzenes, the methyl-ethylbenzenes, the dimethyl-ethylbenzenes, the diethyl-methylbenzenes, which do not require the use of higher temperatures. Mono-, di- and tripropylbenzenes, the η-butyl- If, on the other hand, it has a high reactivity, sec-butyl- and tert-butylbenzenes, the isopropylbenzenes, including cumene and pseudocumene, diisopropylbenzene, mono- and diamylbenzene, didecylbenzene and Benzenes, with mixed alkyl groups, are added with continued stirring so that _{sites, including those with both branched and reactive, are avoided as far as possible, unbranched C 1} to C ₁₃ alkyl groups and preferred if bridging is not possible when referring to C ₁ to Q -Alkyl substituents and the linkage of only two rings remains, the most diverse mixtures of the substances mentioned. Reaction expediently only until implementation

As a bridging component, aldehydes 35 of a part, z. B. about 30% of the applied such. B. formaldehyde, acetaldehyde, propionaldehyde, alkylbenzenes, whereupon the obtained isobutyraldehyde, decylaldehyde, dodecylaldehyde u.
like; Alkynes such as acetylene, methyl acetylene, ethyl acetylene and the like; Diene hydrocarbons, such as ζ. Β.
1,3-butadiene, allene, isoprene, piperylene, dimethyl-40
butadiene and higher dienes; Glycols such as
Ethylene glycol, propylene glycol-1,3, butylene glycol-1,4,
Hexylene glycol-1,6, hexylene glycol-1,2, decylene glycol-1.10, etc .; Haloalkanes, such as. B. all dichloro,
Dibromine or chlorine-bromine compounds which should be made by 45 sators.

the limits of the formula II indicated carbon in the case of the use of dihaloalkanes

number, to be used. As bridging agents, alkylene oxides, such as, for. B. ethylene oxide, propylene chloride or another Friedel-Crafts catalyst oxide or epichlorohydrin, and ketenes into consideration. are the alkylbenzene and the dihaloalkane to-In the industrial implementation can also 50 mixed nearest and usually cooled to about 0 ⁰ C or an aromatic extract of a reforming or below, after which the aluminum chloride in aromatization (Erdölreformat), the overall suitably possibly also quickly, added homely which contains C ₆ to C ₉ aromatics and becomes up to. These reactions are typically 50% benzene or the aromatic bridging agents such as ethylidene dichloride, Bu-C ₇ , C ₈ or C ₉ fractions of such an extract are 1,4-ethylene dichloride, 1,6-hexylidene chloride, isobutylidene will. The C ₈ fraction, containing the 1,2-chloride, butylene bromochloride-1A propylenedibrodrei isomeric xylenes and ethylbenzene, sometimes 1,3-1,2-ethylene dichloride, 2,2-propylene dichloride, together with small amounts of toluene and / or isobutylenedibromide-1,3 and the like, carried out, some C ₉ aromatics, can be carried out very economically.

Way to be used in their entirety. It can be used to remove the o-xylene and residues by decanting, filtering and / or recovering the mixture of m- and p-xylene, washing, optionally using acid. To remove the Friedel-Crafts catalysts, the p-xylene can be separated off from the last-mentioned mixture and the remaining m-xylene can be separated off by washing again with alkali. When used together with the o-xylene. If acidic catalysts are used, it is sufficient to wash the entire C ₈ fraction as well as any wash with water and / or aqueous alkali; Thus, each represents petroleum materials under the conditions used

Reaction products of the formula IV are separated off and the unreacted alkylbenzene is returned to the reaction vessel.

Olefinic compounds are generally not used together with the bridging agents, except where both alkylation and bridging are present in the same reaction a catalyst serving for both reactions

9 10

not to be hydrogenated, they do not need to remove alkylbenzenes with methylene chloride or formaldehyde to become. In this case, all of the obtained and subsequent hydrogenation is the case. So are Get product for hydrogenation. In most cases, for example, in a synthetic di- (methyl However, the unconverted proportions of cyclohexyl) methane fuel, which is produced by hydrogenation removed by distillation, whereupon the mixture of 5 is obtained by condensation of formaldehyde with toluene isomeric compounds of the formula IV is hydrogenated. formed di- (toryl) -methane is formed, six isomers The product can still be present before the hydrogenation. It is di- (2-methyl distilled in order to achieve a larger cyclohexyl) methane, di- (3-methylcyclohexyl) methane, Degree of purity of the products of the side di - (4 - methylcyclohexyl) - methane, (2 - methylcycloreactions, such as B. the tri- and polycyclic io hexyl) - (3-methylcyclohexyl) methane, (2-methylcyclo compounds, to separate. The hydrogenation is hexyl) - (4-methylcyclohexyl) methane and (3-methyl usually in a solvent, e.g. B. a cyclohexyl) - (4-methylcyclohexyl) methane. Paraffinic hydrocarbon, in the presence of a hydride- Four other isomers that occur when others are used

approximately catalyst, such as. B. a nickel or cobalt production process, are the folkatalysator or another aroma for hydrogenation: Di-Cl -methylcyclohexylj-methane, (1-methyltischer Compounds suitable catalyst, from cyclohexyl) - (2-methylcyclohexyl) methane, (1-methyl led. In the examples came active Raney nickel cyclohexyl) - (3-methylcyclohexyl) methane and 1-Me- or Raney cobalt catalysts are used. ethylcyclohexyl) - (4 mg € hylcyclohexyl) methane.

To speed up the rate of hydrogenation, although some really symmetrical "to"

If the hydrogen is usually present with increased bonds, any pressure, usually in the range between 35 and 350 kg / cm ² , of these can only be applied as a small proportion even in simple applications. Also, it will usually be present in the case of an increased most complex mixture of isomers. Temperature, usually between 100 to 200 ⁰ C or so there is, for. B. isomeric di- (methylcyclohexyl) -

worked on until the onset of hydrogenation. methane, but already a hundred and forty-four possible Each aryl ring usually has a lower hydrogenation isomer of dimethylcyclohexyl methane. Of these temperature that depends on the activity of the catalyst may be due to condensation of formaldehyde or and the position of the alkyl substituents in the ring from methylene chloride with a xylene mixture and appends. Obtained thirty-six by selective hydrogenation (choice of final hydrogenation Catalyst activity, temperature, hydrogen pressure.

and optionally solvent) can only be a 30 A typical example of the production of a Hydrogenate ring of the biaromatic ring compound, mixture of isomers according to the present invention where intermediate stages of the formulas is the following:

■. A mixture of o-, m- and p-ethyltoluenes, the

ι ι] can be obtained from petroleum or coal tar,

(R ¹ Jm ■ H --Y - | - - j (R ²⁾ "- VIII 35 when reacted with formaldehyde (eg \ / ~ \ / use of sulfuric acid as a catalyst in!

^ 3O ⁰ C) a di- (methylethylcyclohexyl) methane, the

\ all theoretically possible isomers (hundred) in

Y - iH- ^: - (R ² ) ni IX contains amounts that depend on the relative reaction

X ) / 40 ability of formaldehyde with the four different ones

Hydrogen atoms are formed from each of the ethylene present. In these formulas, R ¹ , R ² , Y, m have toluenes depending.

and η have the same meaning as in formula I. It has been found that the heat of combustion

In the same way, the mixtures of the proportions of the individual isomers in some of the isomeric compounds of the formulas V and VI in such isomer mixtures can also be hydrogenated with some help. is interdependent. For example, each of the partial hydrogenation products produced by hydrogenation of the reaction formula obtained at 30 ° C is an intermediate product as such for the product made from commercially available xylene and the rocket aldehyde (37% formaldehyde) produced during further hydrogenation 50 a heat of combustion of 10.842 kcal / kg, while the hydrogenated acyclic compounds of the ^{formula IV from the same starting materials at 6O 0} C can have a low, less than approximately and then hydrogenated product a 50% of corresponding bridges with heat of combustion of 11.017 kcal / kg. The two unsubstituted cyclohexyl radicals contained in the reaction product of methylene chloride and xylene, a mixture. So z. For example, the one made at Ver 55 using anhydrous aluminum mixture of a mixture of benzene and alkylbenzene chloride, on the other hand, had a heat of combustion of 10,900 kcal / kg after hydrogenation in the bridging reaction. hydrogen with linked unsubstituted phenyl It can thus be stated that the properties of esters cannot be separated from the mixture including the heat of combustion of a given one of the substances of the formula IV before hydrogenation, 60 isomer mixture of di- (mono- or di-alkyls) together with these for hydrogenation cyclohexyl) methanes from the type of production, whereby one also depends on high quality rockets. The constancy of the energy content of a fuel is maintained. The products according to the invention represent, as a significant advantage has already been mentioned, the products according to the invention represent very complex mixtures of different fuels according to the invention, especially in the case of positional isomers, even in the simplest case, use as rocket fuel, since the target when the bridge is through a methylene group is formed calculations are based in part on knowledge of the energy used, for example in the case of condensation of the contents of the amount of fuel added.

refluxed for another hour. About 24 grams of formaldehyde passed through the Reflux condenser lost. The remaining part of the formaldehyde (2.2 mol), which is produced by polymerisation of the 5 Paraformaldehyde was formed under the reaction conditions, condensed with the toluene. the The mixture was cooled, the hydrocarbon layer was separated from the acid and mixed with 2 l of water and then with 2 1 of a 1% sodium carbonate

distilled to remove the excess toluene. The remaining mixture of isomeric di (tolyl) methanes distilled at 11 mm Hg between 137 and

Df = 0.996; Viscosity 0.65 poise at -25 ^C C.

Bp = -65 ° C;

(b) Mixture of the isomeric di- (methylcyclohexyl) methanes

800 g of methylcyclohexane and 58.9 g were added to 294.4 g of the isomer mixture obtained in (a) Raney nickel (Girdler G-49 catalyst, Girdler

The production conditions of the production process according to the invention are easily controllable, so that exactly reproducible products can be obtained with a reproducible heat of combustion. By reacting formaldehyde with a mixture of the three xylenes and the three methyl-ethylbenzenes and subsequent hydrogenation of the condensation product, a fuel was obtained which a large number of isomeric (methylethylcyclo-

hexyl) - (dimethylcyclohexyl) methanes and di- (methyl io solution. The hydrocarbon mixture ethylcyclohexyl) methanes and many more were then initially contained di (dimethylcyclohexyl) methanes at a pressure of 760 mm Hg. The numerous xylyl and ethylphenyl combinations as
Substituents of methane thus increased the number

of isomers in the hydrogenated end products at 15 152 ° C above. The yield was 354 g. Comparison to the hydrogenated reaction products
from xylene and formaldehyde.

Thus, according to the invention, di- (alkylphenyl) methanes by reacting alkylbenzenes or
their mixtures with formaldehyde (using 20
a Friedel-Crafts catalyst at z. B. 5 to
25 ³ C) obtained by hydrogenation in the
Fuels according to the invention are transformed.
Other catalysts and temperatures can be used
Preparation of a hydrogenated end product from ab- 25 Corp.). The mixture was placed in a softening isomeric autoclave with a capacity of about 3.7 liters, which was equipped with a magnet. table stirrer and was equipped with hydrogen

The precursors of the formulas IV, V and VI were ^{filled at 22 °} C. to a pressure of 70 kg / cm ² over Raney nickel (for example Girdler G-49 catalyst). The autoclave was then brought to 120 ° using 8 parts by weight of methylcyclo-30 and was kept at this temperature for 4 hours as the solvent, based on 1 to 4 parts by weight, with constant stirring. During this part of the substance to be hydrogenated, hydrogenated. The hydrogenation time was added three times in addition hydrogen, tion was carried out between 100 and 200 ⁰ C at a wherein the pressure of 28, 35 and 43.7 kg / cm ² are each a hydrogen pressure of 65-100 at in to a pressure of 70 kg / cm ^{2 was} brought. Autoclave with stirring for 2 to 8 hours. After the third addition of hydrogen, the temperature was maintained at 120 to 125 ^° C. for a further 80 minutes at 120.degree. To 125.degree. C. water-clear to pale yellowish fuels. The pressure dropped to 68.2 kg / cm ² and remained during

In the following examples, Gross becomes constant for the last 30 minutes. After the Heat of combustion of a fuel the entire autoclave was filtered and the methylcyclohexane 40 developed during the combustion process is removed by distillation. A mixture was obtained Heat after cooling to the starting temperature of the isomeric di- (methylcyclohexyl) methanes in one (usually 15.56 ° C) assuming that the yield of over 300 g.

total water produced during combustion - C = 87.08%, H = 13, .15%. Kp. 111 to 12O ⁰ C

amount is condensed, understood. Below the net 7 mm Hg; Mp below -7O ⁰ C; Viscosity = 1.4 The heat of combustion of a fuel becomes the 45 poise at -25 ° C; Heat of combustion 11.001 kcal / total amount of heat developed during combustion kg (gross), 10.316 kcal / kg (net), 9.059 kcal / l (net), after cooling to the starting temperature (usually when using 1910 g o-xylene instead

the 1660 g of toluene were obtained as a mixture of di- (o-xylene) methanes, which were hydrogenated to form the di- (1,2-di-50 methyl-cyclohexyl) methanes. In analog 1910 g of m-xylene gave the di- (m-xylene) methanes, which were hydrogenated to the di- (1,3-dimethyl-cyclohexyl) -methanes, 1910 g of p-xylene the di- (p-xylene) -methanes, to the di- (1,4-dimethylcyclo-

200 g of a mixture of 96.7% sulfuric acid 55 hexyl) methanes were hydrogenated, and 1910 g of one (1.973 mol) and 2.8 g of iron (II) sulfate heptahydrate any mixture of two or more xylenes (0, 01 mol) were placed in a glass vessel filled with mixtures of the mixed di- (xylyl) methanes, from a stirrer, a reflux condenser, one of which the mixed di- (dimethyl thermometer) and an opening for the addition of the cyclohexyl) -methane were obtained. Was provided at Verwen reaction components. The vessel 60 dung 1910g of ethylbenzene were the di- (äthylwurde in a water bath at a temperature phenyl) the cooled to the di- (äthylcyclohexyl) -from 18 to 21 ⁰ C methanes. Methanes were added to the mixture, and when using, with stirring, 90 g 1910 g of an aromatic C ₈ fraction of the di- (ge-paraformaldehyde (corresponding to 3 mol of anhydrous mixes C ₈ -alkylphenyl) methanes in the course of 25 minutes that formaldehyde in hydrogenation). Stirring was continued for 60 minutes at 65, di (mixed-Cg alkylcyclohexyO-methane showed a temperature of 25 ^C C and then heated condition.

in the water bath for 2.5 hours at 95 ⁰ C, in the example given, the amount of

was further stirred. Then the mixture of alkylbenzene between 0.5 and 18 mol and more, loading

15.56 ° C) assuming that the water produced during the combustion has not condensed,
Understood.

Example I.

(a) Mixture of the isomeric di (tolyl) methanes
1660 g of toluene (18.04 mol), 96 g of methanol (3 mol),

13 14

based on 1 mole of formaldehyde, can be varied. The p-xylene, 42% m-xylene, 16 ° / ₀ o-xylene, 1.5% higher excess of the alkylbenzene, usually minde- boiling hydrocarbons such. B. ethyl toluene. corresponds at least to twice the molar amount, holds 18 mol (1910 g) of this xylene mixture was sufficiently diluted with the system and pushes the 4 mol of paraformaldehyde, 3 mol of methanol and 4 mol of tricyclic and higher polycyclic dilution 5 96.7% strength Sulfuric acid, the 0.01 mole of iron (II) bonds back. Conversely, when a lower amount of menulphate heptadydrate is used and contains up to 0.5 mol, the amount obtained is higher. The paraformaldehyde was added in the course of the amounts of higher cyclic compounds. That of 25 minutes, during which, the temperature process can be increased gradually from 29 to 59 ° C by separating the hydrocarbons. The temperature and acid layer and renewed supply of the acid to temperature were then slowly brought to about 70 ° C., the system being carried out continuously. which was then stirred for a further hour. Since water is split off in this reaction, the loss of formaldehyde was estimated to be the acid concentration by continuous 29 g or 0.97 mol. 15 game I described, distilled and resulted in 416.3 g of one to be produced. To bind the water formed during the reaction distilling between 152 and 167 ° C / 2mm Hg, phosphorus product and 200 g of a residue on a pentoxide or another water-binding condensation product of di- (xylyl) methane can also be used be added. In the specified by-xylene and formaldehyde, apparently a di- (xylyl) game, paraformaldehyde was used, but methylxylene of the formula VI, where R ₁ and R ₂ = CH ₃ , can also be gaseous formaldehyde or form-Y = CH ₂ , ρ - 2, m = 2 and η = 3. The aldehyde solutions are used. 416.3 g consisted of a mixture of di- (ethyl

Instead of the phenyl) methane, di (xylyl) methane and (xylyl) (ethyl) iron (II) sulfate used as co-catalyst in the example, other phenyl) methane can also be used and provide 1.86 mol of the product Friedel-Crafts compounds of transition metals, 25. The mixture gave the following physical values: z. B. other sulphates, together with sulfuric acid n% ° - 1.5663; Df = 0.978; Bp = -40 ° C; Viscose can be used. The reaction can also be carried out with tat = 27 poise at -25 ° C. The yield was Lewis acid catalysts alone, such as, for example, fluorine-61.5% of theory, based on converted hydrofluoric acid. In this case aldehyde, or 67.5 percent by weight, based on the generally lower temperatures used, of the total amount of the condensation products formed. Particularly suitable catalysts are in

Example II given. Depending on the dilution ( ^b ) mixed di-idimethylcyclohexyO-methane

degree and the acid concentration is the temperature ^{and higher} homologues

accordingly decreased or increased. The reaction 1 mol of the according to Example III, (a) obtained di-

Conditions should be chosen so that the 35 (xylyl) methane (22'4 g) was as in Example I formation Resin-like by-products wrote as little as possible, using 38.8 g Raney contents is, since this is hydrogenated to lower yields of nickel in 800 g of methylcyclohexane. The Temden desired products. temperature was 130 to 134 ° C, the hydrogen pressure

Using 18.04 moles of another alkyl at 24.5 to 52.5 kg / cm ^s . The reaction time was benzene instead of 18.04 mol of toluene, the 40 is 70 minutes. The resulting water-clear product corresponding mixtures of the isomeric di- (alkyl- was obtained from a mixture of three components, phenyl) -methanes, which after hydrogenation namely di- (dimethylcyclohexyl) -metb.an, di- (ethyl corresponding di- (alkylcyclohexyl ) methanes produce. cyclohexyl) methane and (dimethylcyclohexyl) - (ethyl-

cyclohexyl) methane, each component being made up of

B e i s ρ i e 1 II 45 composed of the various positional isomers.

Mixture of di- (tolyl) -methanes ^The product, which in a yield of about 90%

obtained showed the following properties:

The method according to Example I was carried out under conditions of boiling point = 120 ° C./1 mm Hg; Mp = below -70 ° C; repeated use of 3 moles of paraformaldehyde, n% ° = 1.4760; Df = 0.876; Viscosity = 5 poise with 1.5 mol of 78% sulfuric acid 50-25 ° C. as the catalyst. The elemental analysis gave 88.65% C and was used. The paraformaldehyde was in small 13.39% H. The heat of combustion was 10.986 kcal shares added in the course of 3 hours, while per kg (gross), 10.293 kcal / kg (net), 9.149 kcal / 1 which the temperature gradually increases from 20 to 59 ° C (net). When substituted by sulfuric acid-phos was. The sulfuric acid contents were then changed for a further hour with phosphorus pentoxide mixtures (0.33 mol of P ₂ O ₅ , based on an average temperature of 48 ° C. and 55 1 mol of formaldehyde). The di- (tolyl) concentration formed in the reaction during the course of the reaction did not, methane distilled at 174 to 180 ° C / 10 mm Hg. Since the water formed during the condensation It was produced in a yield of less than 5 g Phosphorus pentoxide transformed into phosphoric acid, hold. This example shows the approximate lower one
Limit of the acid concentration to be maintained. 60 ³ HCHO + 6 CH ₃ C ₈ H ₅

- + ■ 3 (CH ₃ C ₆ Hs) ₂ CH ₂ + 3H _a O

B is ρ ie 1 III ( ^a )

(a) Mixture of the di- (xylyl) methanes 3 H ₂ O + P ₂ O ₅ -> - 2 H ₃ PO ₄ (b)

Example I was repeated, but 65 came up. If you work in this way, the catalog is

Instead of toluene, a commercially available synthetic lysator effectiveness of sulfuric acid is much higher.

Xylene mixture of the following composition for the use of hydrofluoric acid

application: 0.5% toluene, 20% ethylene benzene, 20% instead of sulfuric acid for the above

Process are high yields of di (alkylaryl) methanes obtained which, after hydrogenation, give fuels whose heat of combustion is more than 8,988 kcal is 1 each.

Example IV

Ca) Mixtures of di (tolyl) methanes

with hydrochloric acid vapors slowly evolving, stirring was stopped and the glass jar was stopped for 24 hours Left to itself, the ice of the cold bath melted and the temperature gradually increased Room temperature rose. The reaction mixture was then poured onto 700 g of ice and 300 ml concentrated Hydrochloric acid, heated to near boiling point and then cooled to 50 ° C. The hydrocarbon layer was separated, with the same volume

Amount of water distilled. After passing over at 135 to 145 ° C under normal pressure xylene fraction (30 g) was obtained from 2 to 3 mm Hg and 135 to 15O ⁰ C

lation flask
Residue.

about 30 g of a tarry remained

In this example, the toluene was reacted with formalin (37% formaldehyde) instead of the paraformaldehyde used in Example I. 820 g of 89.5% ige io l% iger hydrochloric acid washed and then to sulfuric acid (7.5 mol), the 2.8 g of iron (II) sulfate removal of the unreacted toluene and small heptahydrate (0.01 mol) was added dropwise to a mixture of 1842 g of toluene (20 mol), 200 g of 37% formalin (2.5 mol) and 40 g of methanol (1.25 mol) with stirring. The reaction, a fraction of 118 g of the di (tolyl) methanes at high temperature, was obtained with the aid of a cold water bath to a refractive index of n'S = 1.5680. Maintained in the range of 18 to 29 ° C. The acid was added over the course of 77 minutes. The mixture turned dark purple-red in color during the addition of the acid. Stirring was continued for 20 hours after the addition of the acid at a temperature of 19-21 ° C. The mixture was then diluted with 1 liter of water, the upper hydrocarbon layer was separated off after thorough shaking, washed and distilled in a Claisen-25 was obtained. Flask, with unreacted toluene separated instead of the aluminum used in Example V

and 179 g of di (tolyl) methane, which at 10 mm Hg chlorides can also transition from other Friedel-Crafts catalysts between 149 and 184 ° C. are used. This gives, for example, 95 g of a residue with a refractive index of It ² S = 1.601 _{when using BF 3} , VCl ₄ , BeCl _{2 and the like.} The residue 30 di (tolyl) methane from toluene and methylene chloride consisted of isomers of di (tolylmethyl) toluene. The composition of the fuel used (0.32 mol). Thus, an estimated 1.55 mol of formaldehyde was converted, while 0.95 mol was escaped through the condenser or washed out of the reaction mixture. The yield of di- (tolyl) -35 methane was 59% based on the converted formaldehyde, and the di- (tolyl) methane represented 66% of the aryl-hydrocarbon reaction products. The product obtained showed the following physical properties

(b) Mixtures of the di- (methylcyclohexyl) methanes

100 g of the di- (tolyl) methanes thus obtained were, as described in Example I, hydrogenated, with a Di (methylcyclohexyl) methane from bp 110 to 120/7 mm Hg in practically quantitative yield

hydrogenated isomer mixture is different for each catalyst, but the heat of combustion lies in each case over 8.988 kcal / l.

Example VI (a) Mixed di (xylyl) methanes

Example V was made using one of the commercial properties: n ² S - 1.5618; Df - 0.979; Fp. Unusual xylene mixture, consisting of 2% toluene,

below -65 ° C.
(b) Mixtures of the di- (methylcyclohexyl) methanes

The product was, as described in Example I, hydrogenated in the presence of Raney nickel. One received a fuel with a heat of combustion of over 9.055 kcal / 1. If in the above stated Example xylene (20 moles) are used in place of the toluene, the hydrogenated fuel consists of a mixture of isomers of di- (dimethylcyclohexyl) methanes. If trimethylbenzene (20 moles) in place When toluene is used, the fuel consists of a mixture of the various isomers of Di (trimethylcyclohexyl) methane.

10% p-xylene, 48% m-xyloI, 19% o-xylene and 21% Ethylbenzene, repeated.

(b) Mixed di (dimethylcyclohexyl) methanes

The hydrogenated end product was similar to that obtained according to Example V, but was somewhat inferior Density and a slightly higher heat of combustion.

Example V
(a) Mixtures of di (tolyl) methanes

Example VII (a) Mixtures of the di (xylyl) methanes

The procedure of Example III was repeated, but a xylene was used which was about 90% Contained p-xylene and 10% o- and m-xylene. Because of the tendency to form resinous products with formaldehyde, if the same reaction conditions were observed, lower yields of the desired Obtained di (xylyl) methane isomer mixture.

1 mol of 1,1-dichloromethane (85 g) was weighed into a glass vessel with a capacity of 41, which was provided with a reflux condenser, stirrer, thermometer and dropping funnel. The glass vessel was cooled with ice water. 6 mol of dry toluene (552 g) were then added with stirring. After the temperature of the very slowly stirred mixture had fallen to 5 ° C., approximately V ₂ moles of powdered anhydrous aluminum chloride (65 g) were added over 15 minutes. After adding the aluminum chloride,

(b) Mixtures of the di- (dimethylcyclohexyl) methanes

The product prepared in (a) was hydrogenated to give a fuel of a heat of combustion of more than 8,988 kcal / 1 (net).

Example VII-A (a) Mixture of the di (xylyl) methanes

Using the measures described in Example III, a commercial xylene (from

same composition as indicated in Example VI) reacted with formaldehyde. 40 moles of xylene (4247 g) together with 10 mol of methanol (320 g), 0.02 mol of iron (II) sulfate heptahydrate (5.6 g) and 10 moles of 96.1% strength sulfuric acid (1021 g) in the glass vessel described in Example I. For this one added 10 moles of paraformaldehyde (300 g) over the course of 3 hours and 50 minutes, with stirring and at a temperature of 40 to 45 ° C was maintained. After further stirring for 45 minutes were two more moles of 96.1% sulfuric acid (204 g) were added over the course of 1.5 hours, with during of the addition was heated so that the temperature of the reaction mixture at the end of the acid addition had risen to 52 ° C. The acid layer was removed and the upper layer was first washed with it 11 each of water and 11 3% sodium carbonate solution and then three more times with 1 liter of water each time. The distillation of the hydrocarbon products at 745 mm Hg gave the following fractions boiling above 200 ° C.

fraction ° C / 754mmHg "D yield
G 1 200 to 300
300 to 319
319 to 326
326 to 340
340 to 380 1.5300
1.5560
1.5638
1.5653
1.5710 7.8
26.8
1500.0
106.3
31.7 2 380 to 400 1.5862 158 1 3 > up to 400
Residue 1.5700
Solids 48.8
115.5 4th total quantity 1995.0 5 6th 7 .. 8th

Di- (ethylphenyl) -methane and the (ethylphenyl) - (xylyl) -methane.

The C ₁₇ distillation cut which contained these isomers was hydrogenated as indicated under (b) above and gave a fuel with a heat of combustion of more than 8.988 kcal / l (net).

Example VIII
(a) Mixtures of di- (ethylphenyl) methanes

A glass vessel equipped with a stirrer, reflux condenser, thermometer and feeder was brought to an average temperature of 50 ° C. in a water bath. The reaction vessel was charged with 1910 g of ethylbenzene (18 mol), 406 g of 96.9 ° / _o sulfuric acid (4MoI), 5.3 g of iron (II) sulfate heptahydrate (0,02MoI) and 64 g of methanol (2 Mead). To this, 120 g of paraformaldehyde (4 mol) were added in small portions over the course of 2 hours. The temperature averaged 51 ° C. Stirring was continued for a further half an hour at 50 ° C. During the reaction, the reaction mixture turned dark purple in color. The hydrocarbon layer was decanted, with 11 of water, then with 1 1 3 ^o / oig ^e r aqueous sodium carbonate solution and finally washed with 1 1 water. The unreacted portions were distilled off and the residue was distilled as follows:

35

Fractions 2 to 6 boiling in the range between 300 and 400 ° C, which together weighed 1822.9 g, represented the mixture of isomeric di (xylyl) methanes used as a precursor according to the invention.

fraction 1 . Kp. ⁰ C lmm Hg 1
1 , 5540
, 5541 yield
G 2 148
150
152 up to 150
to 152
Residue 12.2
475
141 3

Fraction 1 was an amber liquid, fraction 2 a clear liquid and fraction 3 a dark red, viscous liquid.

(b) Mixture of the di- (dimethylcyclohexyl) methanes

Hydrogenation of 673 g of Fraction 3 was carried out using the procedure described in Example I. 1800 ml of pentane were used as the solvent in place of the methylcyclohexane. 101 g of Girdler Nickel Catalyst-G-49-A were used as the hydrogenation catalyst. After 16 hours, during which the autoclave was kept at 155 to 195 ° C. and under a hydrogen pressure of 35 to 56 kg / cm ² , no further hydrogen uptake took place. The contents of the autoclave were filtered and the pentane removed by distillation. 662 g of a mixture of the isomeric di- (dimethylcyclohexyl) methanes were obtained which had the following properties: boiling point of the main fraction after renewed distillation 295 to 302 ° C. / 745 mm Hg; n'i = 1.4759; Df = 0.865; Mp below -50 ° C; Viscosity = <0.5 poise at 30 ° C. The heat of combustion was 10.905 kcal / kg (gross).

(c) Mixtures of the di- (C ₂ -alkylphenyl) methanes
and their hydrogenation products

In this example, the procedure given above under (a) was followed, with 2120 g of a xylene mixture and 2120 g of ethylbenzene was used. A mixture of the isomeric di- (xylyl) methanes was obtained,

(b) Mixtures of di- (ethylcyclohexyl) methanes

The combined fractions 1 and 2 were, im

Example 1 described in more detail, hydrogenated. A mixture of the isomeric di- (ethylcyclohexyl) methanes was obtained with a heat of combustion of more than 8.988 kcal / 1 (net).

Example VIII-A
(a) Mixtures of isomeric di (ethylphenyl) methanes

In a pressure vessel equipped with stirrer and cooling jacket 168 g of diphenylmethane (1 mole), 102 g of 97 ° / _o sulfuric acid (1 mole) and 135 g of gaseous boron trifluoride was added. The pressure vessel was connected to an ethylene line and brought to a pressure of 7 kg / cm ² . The contents of the vessel were shaken vigorously while maintaining the reaction temperature at 300 ° C. After the reaction mixture has reached 56 g

Ethylene (2 mol) had taken up, the ethylene supply was turned off, the vessel opened and the Reaction mixture removed. The hydrocarbon layer was separated from the acid layer and Poured onto 1 kg of ice, whereupon it was washed with 1 1 of 3% sodium carbonate solution and 1 1 of water. After unconverted diphenylmethane had been distilled off, a mixture of the isomers of des was obtained Di- (ethylphenyl) methane (or other di- [ethyl

409 707/111

phenyl] alkanes), which contained small amounts of the mono-, tri- (and higher) ethyl-di- (phenyl) -methanes.

(b) Mixtures of isomeric di (ethylcyclohexyl) methanes

40 g of the di- (ethylphenyl) methane (or other di- [ethylphenyl] alkanes) obtained according to (a), 160 g of cyclohexane and 9 g of Raney nickel (Girdler's 49-A catalyst) were placed in an autoclave and hydrogenated at 160 ° C under a hydrogen pressure of 70 kg / cm ² . After the hydrogenation had ended, the catalyst was filtered off and the cyclohexane was distilled off. The fuel obtained was a mixture of the isomeric di- (ethylcyclohexyl) methanes (or di- [ethylcyclohexyl] alkanes) and had a net heat of combustion of more than 8.988 kcal / l.

(c) Mixtures of di (alkylcyclohexyl) alkanes made from benzene or alkylbenzene, one of which is the bridge Y forming compound and an olefin

Instead of the diphenylmethane used in Example (a) above, 2 mol of benzene and 1 mol of a bridging agent, such as. B. a diene hydrocarbon such as butadiene, isoprene, piperylene, their homologues up to and including the C ₁₃ homologues or mixtures thereof (see. Example XVI and XXVII), together or alternating with 1 to 3 moles of an olefin, ζ. Β. Ethylene, propylene, butylene, isobutylene, their homologues up to and including the C ₁₃ homologues or mixtures of these olefins, with the aid of a suitable alkylation catalyst, e.g. B. sulfuric acid and boron trifluoride, as indicated in (a), can be reacted to form the corresponding di- (alkylphenyl) alkanes (formula IV). These can be hydrogenated, as indicated under (b) above, to give an isomer mixture of the corresponding di- (aJkylcyclohexyl) alkanes (formula I) or to give the partial hydrogenation products corresponding to formula VIII or IX.

If di (alkylcyclohexyl) alkanes or di (trialkylcyclohexyl) alkanes with the same or different alkyl substituents on the cyclohexyl radicals are to be prepared, benzene can be used together with two or more olefins and a compound forming the bridge Y. One or more C ₁ - to C ^ -alkylbenzenes together with one or more olefins and a compound forming the bridge Y can also be used. These substances are converted in the same way as indicated in this or the other examples with the aid of an alkylation catalyst into an isomer mixture according to formula IV, from which an isomer mixture according to formula I, VIII or IX (see example XIV-A) is obtained by subsequent hydrogenation. is obtained.

Example IX
(a) Mixtures of isomeric di (isopropylphenyl) methanes

A equipped with a stirrer, reflux condenser, thermometer and dropping funnel provided glass vessel was heated in a water bath to 45 to 50 ⁰ C and then with 480 g of cumene (4 moles), 100 g of 96.9% sulfuric acid (1 mole), 32 g of methanol (1 Mol) and 1.1 g of iron (II) sulfate heptahydrate (0.005 mol) are charged. To this, 30 g of paraformaldehyde (1 mol) were added in small portions over the course of 2 hours. The hydrocarbon layer was then separated, 1 1 3% ^f aqueous sodium carbonate solution and then washed with 1 1 water, after which removed the unreacted cumene by distillation. The product thus obtained was distilled as follows:

fraction At ° Q
745 mm Hg 1.5225
1.5406
1.5407
1.5429
1.5670 Yield*
G 1
2
3
4th
Residue 225 to 325
325 to 335
335 to 340
340 to 350
> 350 10.2
76.7
26.2
21.7
31.8

*) The distillates showed a faint greenish color.

(b) Mixtures of isomeric di (isopropylcyclohexyl) methanes

Fractions 1 to 4 were used for hydrogenation (if desired, the residue can also be added) united. The hydrogenation was carried out as indicated in Example I. The resulting mixture of isomeric di- (isopropylcyclohexyl) methane had a net heat of combustion of more than 8.988 kcal / l.

Example IX-A (a) Mixtures of isomeric di (isopropylphenyl) methanes

In a glass vessel equipped with a stirrer, which was located in a water bath at 2O ⁰ C, 168 g of diphenylmethane (1 mol) and 102 g of 97% sulfuric acid were added (1 mole). To this end, propylene was passed in over the course of 4 hours with vigorous stirring until 105 g (2.5 mol) had reacted. The hydrocarbon layer was then lifted from the acid layer and washed with 1 liter of water, 1 liter of 3% strength aqueous sodium carbonate solution and again with 1 liter of water. Unreacted diphenylmethane was removed by distillation. The product thus obtained consists mainly of di- (isopropylphenyl) methane with a small amount of (isopropylphenyl) - (phenyl) methane and (diisopropylphenyl) - (isopropylphenyO-methane.

(b) Mixtures of isomeric di- (diisopropyl-phenyl) -methanes

The preparation of this mixture of isomers was carried out in the same manner as described in this example in the portion (a), only the reaction temperature by means of maintaining an ice bath at 2 ⁰ C and the propylene in the course of 6 hours or until recording of 172 g of propylene (4 , 1 mole). Thereafter, the acid layer was decanted off and the hydrocarbon layer was washed, whereby di- (diisopropylphenyl) methane was mainly obtained. In Examples IX-A, (a) or (b) ¹ J ₂ mol of boron trifluoride can be added to accelerate the reaction and to change the mixing ratio of the isomers.

(c) Mixtures of (isopropylphenyl) - (phenyl) methane

If 46 g of propylene (1.1 mol) are reacted as in Example IX-A, (isopropylphenyl) - (phenyl) methane is mainly formed.

(d) Mixtures of di (isopropylcyclohexyl) methane

In an autoclave, 20 g of the obtained according to (a), essentially from di- (isopropylphenyl) -me-

than the existing product, 80 g of cyclohexane and 5 g of Raney nickel (Girdler - G-49-A catalyst). The mixture was ^{hydrogenated at 160 °} C. under a hydrogen pressure of 70 kg / cm ² . After filtering off the catalyst and distilling off the cyclohexane, a fuel is obtained which consists of an isomer mixture of the various di- (isopropylcyclohexyl) methanes and has a net heat of combustion of more than 8.988 kcal / l.

(e) Mixtures of the di- (diisopropyl-cyclohexyl) methanes

96.9% sulfuric acid (1.5MoI), 24 g methanol (0.75MoI) and 1.1g ferrous sulfate heptahydrate (0.005 mol). To this end, 45 g of paraformaldehyde (1.5 mol) were added in small portions over 1.5 hours. During the reaction the temperature was an average of 55 ⁰ C. After 0.5h continued stirring, the hydrocarbon was decanted from the acid layer and then finally washed with 1 1 water, 1 1 of aqueous 3 ° / cent sodium carbonate solution, again with 1 1 water, after which the unreacted fractions were removed by distillation. The product was distilled as follows:

fraction Bp ° C / 745mmHg Iff yield
G 1 300 to 350 1.5211 7.9 2 350 to 360 1.5421 131.6 3 360 to 370 1.5451 34.8 4th 370 to 390 1.5511 16.5 5 390 to 395 1.5619 12.4 6th 395 to 405 1.5688 15.0 7th 405 (backlog) Solid 43.0

This example was made similar to Example IX-A, (d), but using 20 g of di (diisopropylphenyl) methane executed. The di- (diisopropylcyclohexyl) methane formed as the hydrogenation product has a net heat of combustion of more than 8,988 kcal / 1.

20th

(f) Mixtures of (isopropylcyclohexyl) - (cyclohexyl) methane

This example was carried out similarly to Example IX-A, (d), except that 20 g of (isopropylphenyl) - (phenyl) methane were used used. As a hydrogenation product

an (isopropylcyclohexyl) - (cyclohexyl) methane is obtained. Fractions 1 to 4 were liquids

th, which is a valuable fuel, and fraction 5 separated a part as a solid, and net heat of combustion of more than 8.988 kcal / l fraction 6 solidified with a melting point of. 30 about 50 ⁰ C.

Instead of the 1, 2 and 4 moles of propylene in Examples IX-A, (c), (a) and (b), oc-isoolefins, such as _(b) mixtures of di- (sec-butylcyclohexyl) methanes, can be used
Isobutylene, isopentylene, isohexylene, diisopropylene, _and higher fractions
Tripropylene, diisobutylene, triisobutylene and the like, or

other «olefins such as ethylene, butene-1, pentene-1, 35. The combined fractions 2 to 5 were used as in hexene-1 and the like. When using Example I described in more detail, hydrogenated. As one of these α-olefins it is sometimes necessary to obtain the active isomer mixture which had a net burnability of the sulfuric acid catalyst due to the addition of thermal energy of more than 8.988 kcal / l.
Boron trifluoride (e.g. 0.6 mol of boron trifluoride to 1 mol
concentrated sulfuric acid [cf. Example VIII-A]) to 40 B eis ρ ie 1 XI

raise. (a) Mixtures of 1,1-di (tolyl) ethanes

Instead of 1 mole of diphenylmethane, 1 mole

of one or more of the diphenyl derivatives of In the glass vessel described in more detail in Example I.

Ethanes, propane, butanes, pentanes, hexanes, iso- of 41 contents were 1658 g of toluene (8 mol) and 406 g butane or any other compound of the 45 96.7% strength sulfuric acid (4 mol). The container Formula VII was cooled to 5 ° C in an ice bath. Under violent

With stirring, 4 moles of acetaldehyde were added dropwise over 35 minutes. The temperature rose to 15 ° C. during the addition. The originally colorless mixture gradually turned orange-red and finally dark brown. A small part of the aldehyde (boiling point 21 ^° C.) was lost through the cooler. Stirring was continued for 85 minutes, the temperature dropping ^{to 3 ° C.} The dark brown mixture was then allowed to warm ^{to 25 ° C.} Since the acid layer could not be easily separated, 400 g of sodium carbonate were added in small portions with simultaneous stirring. During the neutralization, the solution warmed up, some unreacted acetaldehyde still distilling off. The proportions showed that a total of 2.24 mol of the added aldehyde was lost through evaporation. The aqueous layer was removed, the hydrocarbon layer was washed with 1500 ml of water, and then the toluene was distilled off. The toluene-free product was distilled at atmospheric pressure with the following fractions collected:

+ Y-

VII

where Y is an alkane radical having 1 to 13 carbon atoms, can be added. The different Isomers obtained by alkylating agents of the formula VII type give compounds of the type of formula IV, which after hydrogenation [such. B. in Example IX-A, (d) shown] from the various Isomers of the formula I result in existing fuels according to the present invention.

Example X
(a) Mixtures of isomeric di- (sec-butylphenyl) methanes

In a vessel equipped with a reflux condenser, stirrer, thermometer and dropping funnel glass vessel was heated in a water bath at 5O ⁰ C. 805 g of sec-butylbenzene (6 mol), 152 g, were added to the vessel heated in this way

fraction Bp ° C 745 mm Hg n% ° yield
G 1 255 to 298 1.5421 14.0 2 298 to 300 27.1 3 300 to 304 10.6 4th 304 to 306 30.3 5 306 to 308 97.8 6th 308 to 310 55.7 7th 310 to 315 28.7 8th 315 to 325 1.5551 21.0 9 325 to 365 , 5587 18.5 10 365 to 380 , 5601 12.8 11 more resinous , 5611 40.0 Residue , 5620 , 5618 1.5628 1.5618 1.5539 darker Solid

fraction Bp ° C / 2mmHg 1 , 5668 yield
G 1 154 to 164 1 , 5868 555 2 164 to 245
245 back 125
164 3 was standing

silver sulfate and 257 g 97.4% sulfuric acid charged. Commercially available acetylene, containing acetone for stabilization, was passed through a water bottle and then through a sulfuric acid drying column and then introduced into the mixture of toluene and catalyst, where it was quickly absorbed and reacted. The introduction rate of the acetylene was adjusted so that the reaction temperature did not rise above about 15 ⁰ C, ίο In the course of 10 hours was about 4.5 mol acetylene were added (117 g). As the acetylene was absorbed, the mixture gradually changed color through yellow, orange, red and brown to dark brown. After the reaction had ended, 1 l of water was added, whereupon the acid layer was separated off after thorough mixing. The top layer was again with 1 1 of water and then

Fractions 1 to 10 together weighed 316.5 g with 1 liter of 3% strength aqueous sodium carbonate solution and were washed in a temperature range between 255. The hydrocarbon layer was then up to 380 ° C, with the bulk of it being distilled between 298-20 from a Claisen flask. After completion and 325 ° C distilled. All of the distillate had the following properties, the removal of the toluene by distillation: Df = 0.976; nf = 1.5600; follows distilled:
B.p. below -65 ° C; Viscosity = 5 poise at
-25 ° C,

(b) Mixtures of the!, l-Di-Onethylcyclohexyrj-Ethane

Fractions 1 to 10 were pooled and how
described in more detail in Example I, hydrogenated. One received
a mixture consisting of the various isomers of 1,1-di- (methylcyclohexyl) -ethane, which
a density of Df - 0.891, a refractive index
of n'a = 1.4800 and a heat of combustion of
was over 9.055 kcal / l. Fraction 1 consisted of l, l-di (tolyl) ethanes,

If, instead of the 18 moles of toluene, 18 moles (or 35 fraction 2 from di- (I -tolylethyl) -toluenes according to a substantial excess over the stoichiometric formula VI with R ¹ = CH ₃ , m = \, n - 2 and P = I required amount) of a different alkylbenzenes and fraction 3 from higher condensation products uses, one obtains mixtures of the corresponding iso- according to the formulas V and VI.
mers l, l-di (alkylphenyl) ethanes, which, after hydrogenation, give the corresponding!, l-di-alkylcyclohexyl) - 40
ethane surrendered. (b) Mixtures of the l, l-di (methylcyclohexyl) ethanes

The condensation of acetaldehyde with toluene in

Example XI can also be used with boron trifluoride catalysts 210 g of the l, l-di (tolyl) ethanes

or with complex catalysts of boron trifluoride fraction 1, as described in more detail in Example I, and phenol, ether or methanol and the like were carried out 45 using 41 g of Raney nickel (Girdler Werden. A particularly advantageous catalyst is G-49 catalyst ) and 800 g methylcyclohexane hy-phosphorus pentoxide or polyphosphoric acid in hydrogenated form. The hydrogenation time was 3.5 hours and feisäure as these formed during the reaction, the maximum temperature of 261 ⁰ C. After removal binds water and thereby maintains the acid concentration of the catalyst constant by filtration and distilling off. 50 of the methylcyclohexane was a mixture of ver

different isomeric l, l-di (methylcyclohexyl) ethanes

CH3CHO + 2 CH ₉ CH _K (toluene) obtained in practically quantitative yield. The GE

mixed showed the following properties: bp = 174 to 176 ° C / 36mmHg; Mp below -65 ⁰ C. Df = 0.891; nl ° = 1.4816; Gardner viscosity = 5OcP at -5 ⁰ C. Elemental analysis found C 86.65 ° / "and H 13.48 ⁰ I _0th The heat of combustion was 10.936 kcal / kg (gross), 10.230 kcal / kg (net) and 9.103 kcal / l (net).

In contrast to the embodiment described, the acetylene can also initially by a Sulfuric acid-mercury sulphate mixture for the purpose of conversion into acetaldehyde, which then in turn is introduced into the mixture of sulfuric acid and toluene. For practical implementation this process has the advantage that the acid catalyst is retained, since the reaction after runs according to the following scheme.

2 CH ₃ C ₆ H ₅ (toluene)

H ₂ SO ₄

> CH ₃ CH (CH ₃ C ₆ H ₅ ) Jj

P ₂ O ₅ + 3 H ₂ O

2HPO,

H ₂ O (D.

(2)

With such a catalyst higher yields based on the weight of the used Sulfuric acid.

B is ρ ie 1 XII
(a) Mixtures of the l, l-di (tolyl) ethanes

A glass jar of 41 chilled in an ice bath Contents were with 1196 g of toluene (13 mol, 14 g of mercury

Level a

1 mole of acetylene + 1 mole of water
Hg-SaIz

H ₂ SO ₄
Level B.

1 mole of acetaldehyde + 2 moles of toluene
HLSO.

-> 1 mol l, l-di (tolyl) ethane + 1 mol water

To the extent that the water is consumed in stage A, the acid is diluted with it in stage B. Water. Therefore, if equal volumes of 97% sulfuric acid are used to carry out reaction stages A and B, the content of the acid in Level A increased to 100%, while at the same time it decreased to 94% in Level B. The amounts of acid are then exchanged, whereupon the process repeats itself. When the 94% sulfuric acid in Stage A is converted into 100% sulfuric acid and in stage B the 100% sulfuric acid is converted back to 94% has fallen, the amounts of acid are exchanged again in the two process stages. Instead of Toluene can of course also be used other alkylbenzenes, as shown in the table in Connection to example XI is detailed.

Example XIII
(a) Mixtures of the isomeric l, l-di (tolyl) ethanes

This example, which is otherwise similar to Example XII, shows the influence of the use of higher temperatures during the uptake and reaction of the acetylene. 2.27 mol of acetylene were taken up at a temperature between 10 and 28 ^° C. in the course of 3.75 hours. The yield of (a) a mixture of the various isomers of 1,1-di (tolyl) ethane was 58% of theory, based on converted acetylene; the yield of (b) higher condensation products was 42%. Fraction (a) had a boiling point of 214 to 244 ° C./90 mm Hg; a refractive index of n ^! § = 1.5600 and a density of Df = 0.967.

(b) Mixtures of the l, l-di (methylcyclohexyl) ethanes

The hydrogenation of fraction (a) under the conditions given in Example I gave a mixture of the various isomeric 1,1-di- (methylcyclohexyl) methanes in almost quantitative yield, which showed the following physical properties: bp = 167 ° to 185 ° C / 36mm Hg; Mp. Below -65 ⁰ C; Df = 0.890; N% ° = 1.4895; Viscosity = 32OcP at -2O ⁰ C; the combustion energy was 10.869 kcal / kg (gross), 10.163 kcal / kg (net) and 9.031 kcal / 1 (15.6 ° C) (net).

Instead of the sulfuric acid in the example given, under otherwise identical conditions complex compounds of boron trifluoride with water, alcohols, phenols, ethers, acids, etc. in the presence a mercury compound, such as. B. Mercury Oxide, Mercury Acetate or Mercury Sulphate, be used. In these cases, to facilitate initiation of the reaction, the addition of a Trace of water is recommended.

Example XIV
(a) Mixtures of the l, l-di (tolyl) ethanes

Example XII was made using a

1 mol of acetaldehyde .5 mixture of ethylene and acetylene (ratio 40: 60) repeated. The gas mixture, containing 0.465 mol of acetylene (12.1 g), was mixed with 828 g of toluene (9 mol), 119 g of 97.3% sulfuric acid (1.28MoI) and 7 g Mercury sulfate (0.023 moles) at a temperature

ίο implemented from 4 to 6 ⁰ C for 2 hours. After the reaction had ended, the reaction mixture was poured into 700 ml of water. The hydrocarbon layer was separated, washed acid-free and distilled. A mixture of the various isomers of l, l-di (tolyl) ethane was obtained in a yield of 88%. based on the absorbed acetylene. The mixture showed the following properties: bp - 115 to 123 ° C / 1 mn-Hg; nf = 1.5665.

(b) Mixtures of l, l-di- (methylcyclohexyl) ethanes The hydrogenation of the isomer mixture among the

The conditions described in Example XII gave a similar high-energy fuel from a mixture of the different isomers 1,1-di- (methylcyclohexyty-ethane duration.

Example XIV-A

(a) Mixtures of the l, l-di (ethyfmethylphenyl) ethanes

The procedure described in Example XIV was repeated using 368 g of toluene (4 mol), 408 g of 97% strength sulfuric acid (4 mol) and 68 g of boron trifluoride Q mol). 112 g of ethylene (4 mol, as described in Example VIII-A) were introduced into a pressure vessel, after which 26 g of acetylene (1 mol) were gradually added and reacted. The product obtained was worked up as described in Example XIV and resulted in a mixture consisting mainly of isomeric 1,1-di- (ethylmethyl-

phenyl) ethanes. .

(b) Mixture of isomeric l, l-di (ethylmethylcyclohexyl) ethanes

The l, l ~ di- (ethylmethylphenyl) -ethane obtained according to (a) were hydrogenated as in Example XII, (b). The reclaimed product essentially passed from a mixture of isomers of l, l-di- (äthylmethylcyclohexyl) -ethane, which is a heat of combustion of more than 8,988 kcal / l (net).

Example XV
(a) Mixture of isomeric l, l-di (tolyl) ethanes

Example XIV was repeated without the use of ethylene. 11.1 g of acetylene became a mixture the isomeric l, l-di- (tolyl) -ethane obtained in a yield of 90%.

nl ⁰ = 1.5650; Df = 0.981; Mp below -65 ⁰ C. Viscosity = 50 poise at -25 ° C.

(b) Mixture of isomeric 1,1-di- (methylcyclohexyl) -

ethane

The hydrogenation of 84 g of this product was carried out between 100 and 180 ^° C. under a hydrogen pressure of 49 to 77 kg / cm ² in the presence of Raney nickel (16.8 g). The hydrogenation time was 6 hours. After filtering off the catalyst and

409 707/111

Distilling off the methylcyclohexane gave a mixture of the isomeric 1,1-di (methylcyclohexyl) ethanes in a yield of about 90%. Without further fractionation, the product showed the following properties: Df = 0.891; nl ° = 1.4815; Mp below -65 ⁰ C. Viscosity = 5 poise at -25 ° C; Heat of combustion 10.022 kcal / kg (gross), 10.316 kcal / 1 (net).

Example XVI
(a) Mixture of the l, l-di (xylyl) ethanes

IO

1378 g of a xylene mixture (13 mol) of the same composition as in Example VI were mixed with 104 g of acetylene (freed from acetone) in the presence of 257 g of 97.4% strength sulfuric acid and 14 g of mercury sulfate over the course of 7 hours at a temperature of 5 implemented up to 12 ° C. A mixture was obtained in a yield of 57% which contains the l, l-di- (xylyl) -ethanes, l, l-di- (ethylphenyl) -ethanes, ao 1 - (XyIyI) -1 - (ethylphenyl) - Ethane and, in small amounts, the analogous compounds with tolyl substituents. The mixture showed the following properties: bp = 136 to 160 ° C / 4 mm Hg; n * g = 1.5665.

35 Example XVIII

(a) Mixtures of isomeric 1,2-di (isopropylphenyl) ethanes

A glass vessel with a capacity of 4 l, provided with a reflux condenser, stirrer, thermometer and a feed opening, was cooled in an ice bath and charged with 720 g of cumene (6 mol) and 85 g of 1,2-dichloroethane (1 mol). After the temperature had fallen to 5 ° C., 65 g of freshly sublimed aluminum chloride (0.5 mol) were added in small portions over the course of 15 minutes, with evolution of hydrogen chloride. The mixture was turned off overnight, the temperature gradually rising to room temperature after the ice had melted in the cold bath. The reaction mixture was then poured onto 700 g of ice and 30 ml of concentrated hydrochloric acid and heated under reflux. Thereafter, the hydrocarbon layer was cooled to 5O ⁰ C, separated, then washed first with 1 l of 1% hydrochloric acid and then with 1 1 of water. The unreacted cumene was then distilled off. A hydrocarbon mixture was obtained which essentially consisted of the isomeric 1,2-di (isopropylphenyl) ethanes.

(b) Mixture of 1,1-di- (dimethylcyclohexyl) -ethanes _{(b) Mixtures of} ,, 2-di- (isopropylcyclohexyl) -ethanes

238 g of the product obtained in (a) were dissolved in 800 g of methylcyclohexane in the presence of 48 g of Raney nickel, as described in more detail in Example I, under a hydrogen pressure of 70 to 91 kg / cm ² and in a temperature range between 140 and 214 ° C hydrogenated for 6 hours. The processed fuel (yield 95%) showed the following properties: Bp = 136 to 141 ° C / 2mm Hg; Mp below -70 ⁰ C, Df = 0.893. nf = 1.4845; Viscosity = 50 cP at 2O ⁰ C or 98.5 poise at -3O ⁰ C. The elemental analysis showed C = 86.90% and H = 13.52% The heat of combustion was 10.961 kcal / kg (gross), 10.253 kcal / kg (net) and 9.140 kcal / 1 (net).

Example XVII
(a) Mixtures of 1,2-di (tolyl) ethanes

Example XI was repeated using ethylene glycol in place of acetaldehyde. To a mixture of 1244 g of toluene (13.5 mol) and 609 g of 97.3% strength sulfuric acid (6 mol), 186 g of ethylene glycol (3 mol) were added over the course of 3 hours, the temperature of the mixture being between 2 and 4 ° C was held. After completion of the addition was warmed to 4O ⁰ C and maintained for 1.5 hours at this temperature. One then separating the acid layer, washed the upper layer with 1 1 of water and then with 1 l 1% strength sodium carbonate solution ^it. When the washed product was distilled, the unreacted toluene was removed and a mixture of the isomeric di (tolyl) ethanes with a refractive index of Ti ² S = 1.5371 was obtained.

(b) Mixtures of the 1,2-di (methylcyclohexyl) ethanes

By hydrogenation of the 1,2-di- (tolyl) -ethane under the conditions given in Example I was a high-energy fuel obtained from a mixture of the isomeric 1,2-di- (methylcyclohexyl) -ethane duration.

The l, 2-di- (isopropylphenyl) -ethane containing product was in the presence of Raney nickel and methylcyclohexane, as described in more detail in Example I, hydrogenated to give a fuel after removal of the catalyst and the methylcyclohexane from a mixture of the isomeric 1,2-di- (isopropylcyclohexyl) -ethane consisted of a combustion heat of more than Had 8,988 kcal / 1 net. In Example XVIII, the 720 g of cumene (which is a substantial excess over the stoichiometric required amount) can be replaced by any other alkylbenzene. the the resulting di- (alkylphenyl) ethanes differ in that the ethane bridge is in the Substituted 1,2-positions instead of 1,1-position is. Accordingly, the hydrogenation products obtained therefrom are in the 1,2-positions instead of in substituted for the 1,1 positions. In the further exemplary embodiments just mentioned such alkylbenzenes are used in which the total number of carbons of the alkyl group or groups on the benzene ring is one to five. However, such alkylbenzenes can of course also be used are used, the alkyl groups of which have 6 to 13 carbon atoms. Instead of the Examples of alkylbenzenes with two alkyl groups on the benzene nucleus can also include alkylbenzenes, which have three different alkyl groups can be used. Finally, instead of the The uniform alkylbenzenes listed in the examples also include mixtures of different alkylbenzenes with one another or of one or more alkylbenzenes with benzene in the same way as starting materials for the preparation of the isomer mixtures serving as intermediates and their hydrogenation products are used.

Example XIX

(a) Mixtures of the l, l-di (toyl) propane
1658 g of toluene (18MoI) and 162.4 g of propionaldehyde (2.8MoI) were obtained with the aid of 406g of 97.6% strength

Sulfuric acid (4 mol), as described in Example XI, condensed. The reaction was carried out with stirring in a glass vessel cooled with ice. The propionaldehyde was added dropwise in the course of 125 minutes, keeping the reaction temperature was maintained at 6 to 1O ⁰ C. After adding the aldehyde, the mixture was left to react for a further 25 minutes, then the hydrocarbon layer was separated off, washed acid-free and distilled. The yield of the mixture of isomers of the 1,1-di (tolyl) propane was 144.5 g (yield 23%) and about 78 g of l- (tolyl) propane (yield 18%).

The mixture of 1,1-di (tolyl) propanes showed the following properties: Bp = 275 to 375 ° C / 760 mm Hg; ni ° = 1.5310; Df = 0.958; Mp below -65 ⁰ C.

(b) Mixtures of the!, l-DHmethylcyclohexylJ-propane

100 g of the 1,1-di (tolyl) propane mixture were hydrogenated with 20 g of Raney nickel under a hydrogen pressure of 70 kg / cm ² and at a temperature between 200 and 236 ^° C. for 24 hours. The worked-up mixture of the isomeric l, l-di (methylcyclohexyl) propane showed the following properties: Bp = 285 to 330 ° C / 760 mm Hg; n% ° = 1.4790; Df = 0.891; Mp below -65 ° C; Viscosity = 35 Poise at -25 ° C. The heat of combustion was 10.790 kcal / kg (gross); 10.175 kcal / kg (net) and 8.966 kcal / 1 (net).

When using other alkylbenzenes instead of the toluene mentioned in Example XIX, the corresponding l, l-di (alkylphenyl) propane are converted.

Example XX
(a) Mixtures of the l, l-di (xylyl) propane

1698 g of a xylene mixture (16 mol) of the composition mentioned in Example VI (Sinclair Petrochemicals Inc.) were mixed with 169 g of propionaldehyde (2.9 mol) using 507.5 g of 97.4% strength sulfuric acid (5 mol) as a catalyst implemented. The reaction vessel was cooled with ice and the reaction temperature was maintained at 3 to 4 ° C. during the addition of the propionaldehyde, which took place over 5.6 hours. After the addition the mixture was stirred one another 0.9 hours at 2 ° C. After removal of the excess xylenes by the distillation were 50 g of a 165-300 ⁰ C at 745 mm Hg for continuous product were obtained, the following properties which had: nl = 1 °, 5500; Df = 0.970; Mp = -54 ° C; Viscosity = 85 cP at 35 ° C; 15 g of a dark-colored residue remained. The main fraction consisted of 1.6 mol of 1,1-di- (xylyl) -propane in a mixture with l, l-di- (ethylphenyl> propanes and l- (xylyl) -l- (ethylphenyl) propane.

(b) Mixtures of the 1,1-di (dimethylcyclohexyl) propanes

285 g of the product obtained according to (a) with 52 g of Raney nickel (Girdler's catalyst-G-49) at 200 to 236 ^° C. in the presence of 800 g of methylcyclohexane as solvent by the process described in Example I gave about 90% ig ^he yield of a hydrogenated fuel, which consisted of l, l-di- (dimethylcyclohexyl) propane in a mixture with l, l-di (ethylcyclohexyl) propane and l- (dimethylcyclohexyl) -l- (ethylcyclohexyl) propane. The mixture of the different isomers showed the following properties: b.p. = 300 to 400 ° C. / 745 mm Hg; Mp below -65 ° C; Df = 0.907; n% ° = 1.4988; Viscosity = 0.5 poise at 31 ⁰ C, 148 poise at -25 ⁰ C; Heat of combustion 10.847 kcal / kg (gross), 10.136 kcal / kg (net) and 9.176 kcal / 1 (net).
5

Example XXI

(a) Mixture of 1,2-di (xylyl) propanes

In one with reflux condenser, stirrer, thermometer

ίο and supply port provided glass vessel of 41 content, which was kept in a water bath at 20 ⁰ C, was added 848 g of a xylene mixture, 120 g of freshly sublimed aluminum chloride (0.9 mole) and added in the course of 2.5 hours 226 g of 1 , 2-dichloropropane (2 mol) is added dropwise. The temperature remained during the addition at 25 ⁰ C. The reaction vessel was then removed from the water bath, heated to 37 ⁰ C by means of an electric heating mantle and the reaction component with stirring for 2.5 hours at 35 ° C. The reaction mixture was then diluted with 1 liter of a xylene mixture and 50 ml of concentrated hydrochloric acid, poured onto 2 kg of ice, heated to reflux temperature and the hydrocarbon layer was separated off. After washing the hydrocarbon layer with 1 liter of water containing 25 ml of concentrated hydrochloric acid, and washing it further twice with 11 liters of water each time, the excess xylene was removed by distillation under atmospheric pressure. The residue was distilled as follows.

fraction Bp ° C / 745mtnHg 1.5001
1.5069
.1,5501
1.5532
dark oil yield
G 1
2
3
4th
5 165 to 200
200 to 300
300 to 375
375 to 405
405 (backlog) 56.7
36.5
136.4
6.8
6.0

Fractions 1 and 2 consisted essentially of the isomeric Mono-xylylpröpanen, while the Fractions 3 and 4 contained the mixture of the isomeric 1,2-di (xylyl) propane.

(b) Mixture of
1,2-di (dimethylcyclohexane) propane

The 1,2-di- (xylyl) -propanes were converted into hydrogenation according to that described in Example I. Method obtained a fuel which had a heat of combustion of more than 8.988 kcal / 1 (net). In the same way as described above under (a) and (b), other isomer mixtures can also be used are obtained, these differing only in that the propylene bridge is in the 1,2-position and is not substituted in the 1,1-position.

Example XXII
(a) Mixtures of the 2,2-di (tolyl) propanes

368 g of toluene (4 mol) and 134 g of freshly sublimed aluminum chloride (1 mol) were placed in a glass vessel with a capacity of 41%, which was provided with a reflux condenser, stirrer, thermometer and dropping funnel and was in a water bath at 20 ^{° C.} To this was added 113 g of 2,2-dichloropropane (1 mol) dropwise over 2 hours with vigorous stirring. Then the temperature was

increased to 35 ° C and stirred for a further 2 hours. The reaction mixture was, as indicated in Example XXI, processed, only half of the substances specified there were used.

The distillation gave a mixture of the different isomers of 2,2-di- (tolyl) -propane.

the

(b) Mixture of the 2,2-di (methylcyclohexyl) propanes

The 2,2-di (tolyl) propane fractions were hydrogenated in the manner indicated in Example I and gave io (net), a suitable fuel mixture of the isomeric 2,2-di- (methylcyclohexyl) propane, which has a net heat of combustion of more than 8.988 kcal / l and had excellent thermal resistance.

In Example XXII, the 368 g of toluene can be replaced by any other alkylbenzene. the end the products thus obtained can be obtained by hydrogenation (di- (alkylcyclohexyl) propane, which in 2,2-position of the propane bridge are substituted. In the examples just mentioned, alkylbenzenes were used with a total carbon number of the alkyl group or groups of one to five is used. Of course however, in the same way, alkylbenzenes with a total carbon number of Alkyl group of six to thirteen can be used. In the examples, alkylbenzenes were also used used two different alkyl groups on the benzene ring. However, alkylbenzenes can also be used in their place with three different alkyl groups on the benzene ring can be used. Finally you can also instead of the uniform alkylbenzenes used in the examples, mixtures of two or use several alkyl benzenes or mixtures of one or more alkyl benzenes with benzene.

(b) Mixtures of di- (dimethylcyclohexyl) propanes

Fractions 2 to 5 were combined to give the mixture of the various isomeric di (xylyl) propanes. The hydrogenation of this fraction mixture according to the method described in Example I. resulted in a very energy-rich fuel with a heat of combustion of more than 8,988 kcal / 1

(c) Mixtures of 1,3-di (xylyl) propanes

Instead of 4 moles of 1,2-propylene oxide were 304 g 1,3-propanediol (4MoI) used. Furthermore the reaction was carried out in the same manner as indicated in (a) above. A mixture was obtained of the isomeric 1,3-di (xylyl) propane.

(d) Mixtures of 1,3-di- (dimethylcyclohexyl) propanes

Example XXIII (a) Mixtures of the di (xylyl) propanes

1700 g of a xylene mixture (26 mol) containing 19% o-xylene, 48% m-xyloI, 10% p-xylene, 2 ° / _? Toluene and 21% ethylbenzene were reacted under the conditions given in Example XI with 232 g of 1,2-propylene oxide instead of paraformaldehyde in the presence of 406 g of 96.98% strength sulfuric acid (5 mol). The propylene oxide was fed in dropwise over the course of 3 hours, stirring being carried out and the temperature being kept between 10 and H ⁰ C by cooling in an ice bath. The mixture was then heated, stirring was continued for a further 2 hours and the temperature was kept between 40 and 52 ^° C. During the addition of the propylene oxide, a slight orange color first appeared and then a purple color which turned deep orange during heating.

After separation, the hydrocarbon layer became aqueous first with 1 liter of water, then with 1 liter of 3% strength Washed sodium carbonate solution, whereupon the excess xylenes were removed by distillation. The following fractions were obtained:

35 The mixture of 1,3-di- (xylyl) -propane was, as given above under (b), hydrogenated and gave a mixture of the isomeric 1,3-di- (dimethylcyclohexyl) propane, which is a very energy-rich fuel with a heat of combustion of more than 8,988 kcal / 1 represented.

Other mixtures can be prepared in the same way as indicated above under (c) and (d). she differ only in that the propylene bridge is not substituted in the 1,1, but in the 1,3 position is.

Example XXIV

(a) Mixtures of the l, l-di (tolyl) butanes

40

45 1566 g of toluene (17MoI) were reacted under the conditions given in Example XI with 288 g of n-butyraldehyde (4 mol) using 500 g of 96.7% strength sulfuric acid (5 mol) as a catalyst. The aldehyde was added over the course of 3.5 hours, the temperature being kept ^{at 3 to 6 ° C. by cooling in an ice bath.} The mixture was diluted by further stirring for 2 hours at 3 to 6 ⁰ C with 1500 ml of water and worked as described in Example XI, on. The unreacted toluene and residual butyraldehyde were removed by distillation. The residue resulted in the following fractions:

55 ° C / 745mm Hg

163 to 300
320 to 365
Residue

1.4644 to 1.4703

1.5228 to 1.5469

dark solid

Gram

97.8

312.6

23.3

fraction Bp. ⁰ C /
745 mm Hg 1.4970
1.4989
1.4998
1.5100
1.5260 yield
G 1
2
3
4th
5 154 to 177
177 to 205
205 to 232
232 to 260
260 to 288 36.2
14.2
18.0
14.6
9.4

Fraction 3 had a density of Df of 0.956 and, on analysis, showed the values to be expected for a mixture of isomeric 1,1-di- (tolyl) -butanes. Fraction 1 appeared to contain a small amount of 1-tolylbutane and 1-tolyl-octane. The amount of butyraldehyde reacted was 3 mol, while a further mol could be recovered from the reaction mixture by distillation. Based on 3 mol of butyraldehyde, the yields were approximately as follows: 43% 1,1-di- (tolyl) -butane, 22% 2-tolylbutane, 4% higher condensation products.

(b) Mixtures of the 1,1-di (methylcyclohexyl) butanes

119 g of the di (tolyl) butane thus obtained were, as described in more detail in Example I, in 800 g of methylcyclohexane with 24 g of Raney nickel (Girdler 49 A catalyst) under a hydrogen pressure of 70 kg / cm ² 100 to 21O ⁰ C was hydrogenated. 144 g of an isomer mixture of 1,1-di (methylcyclohexyl) butanes were obtained, which corresponded to a practically quantitative yield.

The mixture showed the following properties: b.p. 300 to 330 ° C / 745 mm Hg; n% ° = 1.4798; Df = 0.884; Mp below -65 ° C; Viscosity = 98.5 poise at -25 ° C; Heat of combustion 10.914 kcal / kg (gross), 10.203 kcal / kg (net) and 9.004 kcal / 1 (net).

Similar products were obtained when anhydrous hydrofluoric acid was used in place of sulfuric acid obtained, but the ratio of the individual isomers to one another was different.

Example XXV (a) Mixtures of the 1,1-Di- (xylyl) -butanes

137 g of butyraldehyde (1.9 mol) were mixed under the conditions given in Example X with 1910 g of a commercially available xylene mixture (18 mol) of the composition given in Example VI in the presence of 96 g of methanol (3 mol), 408 g of 96, 7 ° / _o sulfuric acid (4 moles) and 2,2-iron (II) sulfate (0.01 mol). The aldehyde was added to the mixture heated to 73 to 87.degree. C. over the course of 45 minutes. The mixture was then stirred for a further 3 hours at the same temperature and finally for a further 15 minutes at 75 to 85.degree. After the unreacted xylene had been distilled off, the following fractions could be obtained:

Example XXVI (a) Mixtures of the di (tolyl) butanes

In a vessel equipped with a stirrer and in an ice-salt mixture from -6 to -9 ° C chilled glass vessel was charged with 2211 g of toluene (24 mol) and 406 g of 96.9 ° / _o sulfuric acid (4 mol). A slow stream of cooled, gaseous butadiene was passed into the stirred toluene-sulfuric acid mixture in the course of 35 minutes. The butadiene stream (a total of 60 g were fed in) was adjusted so that the temperature of the reaction mixture was kept at −2 ° C. During the reaction the color changed from green to orange. The hydrocarbon layer was decanted off, washed with 1 liter of water, then with 1 liter of 3% strength aqueous sodium carbonate solution and then again with 1 liter of water, whereupon the toluene was distilled off. The residue was subjected to distillation as follows:

fraction Bp. ⁰ C /.
745 mm Hg riS yield
G 200 to 250
250 to 300
300 to 320
320 to 325
325 to 330 1.5058
1.5226
1.5381
1.5458
1.5480 11.2
16.3
12.3
18.1
28.0 2 330 to 335
335 to 340
340 to 350
350 to 360
360 to 380
380 to 400 1.5498
1.5512
1.5524
1.5525
1.5540
1.5561 28.3
8.4
15.2
11.8
18.0
16.3 3. 400 to 405
Residue 1.5561 10.2
13.7 4th 5 6th 7th .. 8th 9 10 12th 13th

Bp ° C / 2mtnHg

38 to 92
92 to 130
Residue

1.4951 to 1.4964

1.5110 to 1.5280

dark solid

Gram

258.9

105.6

84.0

45

Fraction 1 had the bromine number 0 and showed the properties expected for 1-xylyl-butane. Fraction 2 consisted of the desired 1,1-di- (xylyl) -butane. Its density was Df = 0.922, the refractive index was determined to be n'§ - 1.5248.

(b) Mixtures of the di- (dimethylcyclohexyl) -butanes

80 g of fraction 2 were, as described in Example I, hydrogenated with 16 g of Raney nickel (Girdler G-49 catalyst) at 100 to 130 ^° C. under a hydrogen pressure of 80.5 kg / cm ² . After removal of the methylcyclohexane used as solvent, 62.1 g of the hydrogenation product could be obtained, which is obtained from a mixture of the various isomeric l, l-di- (dimethylcyclohexyl) -butane and 1,1-di- (ethylcyclohexyl) -1 - ( ethylcyclohexyl) - butane and showed the following physical properties: Bp = 300 to 355 ° C / 760 mm Hg; nf = 1.4805; Df = 0.875; Viscosity == 148 poise at -25 ⁰ C; Heat of combustion 10.845 kcal / kg (gross), 10.130 kcal / kg (net) and 8.849 kcal / 1 (net).

In this reaction isomers (a) tolylbutanes, (b) tolyldibutanes, (c) die- (tolyl) -butanes, (d) (methyl-butenyl-phenyl) - (tolyl) -butanes and (e) di- (tolyl) -butyl) - (tolyl) -butane obtained. It is assumed that the ^{fractions boiling between 200 and 300 °} C. contain the isomers of type (a) and (b). The fractions boiling between 360 and 405 ^° C. contain the isomers of type (d) and (e).

(b) Mixtures of 1,1-di (methylcyclohexyl) butanes

Hydrogenation of the combined fractions 1 to 12 in the manner described in Example I gave a Isomeric mixture of di- (methylcyclohexyl) -butane, which has a heat of combustion of more than 8,988 kcal / 1 (net).

Instead of the 60 g of butadiene used in the example or the 288 g of n-butyraldehyde used in Example XXV, the following bridging agents can also be used: 1,2-butadiene; monounsaturated Q-alcohols, such as. B. l-butenol-3 (methyl vinyl carbinol), l-butenol-4 (allyl carbinol); C ₄ acetylenes, such as, for example, 1-butyne (ethyl acetylene), 2-butyne (dimethylacetylene); C ₄ -DJoIe, such as B. 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 2,4-butylene glycol, or C ₄ alkylene oxides, such as. B. 1,2-butylene oxide or 2,3-butylene oxide, and mixtures of the aforementioned compounds. If, instead of the Lewis acids, a Friedel-Crafts catalyst, such as. B. aluminum chloride is used

409 707/111

Q-dichlorides, such as. B. 1,1-dichlorobutane, 2,2-dichlorobutane, 1,2-dichlorobutane, 1,3-dichlorobutane, 1,4-dichlorobutane or 2,3-dichlorobutane, or corresponding bromine compounds or mixed C ₄ -Chlor-BrOm- Compounds or mixtures thereof are used.

Example XXVII (a) Mixtures of the di (tolyl) pentanes

Example XXVI was prepared using 204 grams of piperylene (3MoI) in place of the 60 grams of 1,3-butadiene repeated. The piperylene was added over 3 hours and 45 minutes, with the Temperature was kept at 2 ° C. In the course of the reaction the color changed to deep orange. the Hydrocarbon layer was separated by washing with water and alkali from acid residues and then freed from residual toluene by distillation.

The residue was like Kp. "Claim ed follows fractionally: yield
G fraction 101 to 105/15
110 to 112/15
178 to 180/13
187 to 190/13
190/13 * n% ° 23.7
6.7
49.0
27.2
212.0 1
2
3
4th
5 1.5040
1.5080
1.5351
1.5400
fl. residue

Atoms of matter alone or in mixtures can be used as bridging agents.

Example XXVIII (a) Mixtures of (tolyl) undecenes

In a glass vessel with a capacity of 41, equipped with a reflux condenser, stirrer and thermometer, which is in Maintaining a water bath gave 685 g of toluene

ίο (7 mol) and 102 g of 96.19% sulfuric acid (1 mol) given. To this, 169 g of undecylenic aldehyde (1 mol) were added dropwise over 75 minutes. While After the addition of the aldehyde, the temperature rose from 32 to 41 ° C. This was followed by another 50.7 g of 96.19% sulfuric acid are added dropwise (0.5 mol) over 1 hour and 15 minutes, the temperature dropping to 33 ° C. The hydrocarbon layer was separated with 11% water, 11% aqueous sodium carbonate solution and washed 1 l of water, whereupon the unreacted toluene was removed by distillation. The residue was distilled as follows:

25th fraction Bp. ⁰ C /
745 mm Hg * ¥ yield
G 1 380 to 390
390 to 400 1.4819
1.4900 18.1
15.3 2 400 to 409
Residue 1.5185 27.1
about 30 3 30th 4th

* Piston temperature 400 ⁰ C.

Fractions 1 and 2 were amber liquids, Fractions 3 and 4 were navy blue Liquids and the undistillable residue is a viscous amber liquid. The fractions 1 and 2 contained tolylpentane, fractions 3 and 4 the various isomeric di (tolyl) pentanes and (pentenyl-tolyl) - (tolyl) -pentanes.

(b) Mixtures of the di (methylcyclohexyi) pentanes

The hydrogenation of fractions 3 and 4 under the conditions given in Example I gave a Mixture of the isomeric di- (methylcyclohexyl) -pentanes and (methyl-amylcyclohexyl-methylcyclohexyl-pentanes, that had a heat of combustion of more than 8.988 kcal / l.

Instead of piperylene as a bridging _{agent, other aliphatic C 5} dienes, such as. 1,2-pentadiene, 1,4-pentadiene, 2,3-pentadiene, isoprene; C ₆ dienes and higher dienes, such as B. 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,5-hexadiene, Hexadiene-3,4,2,3-dimethyl-butadiene and higher homologues of these dienes with 7 to 13 carbon atoms can be used. Aldehydes, diols, monounsaturated carbinols, alkylene oxides and in some cases reactive saturated and unsaturated ketones with branched or unbranched C _{5 -C 13} carbon chains and mixtures of the substances mentioned can be used as bridging agents instead of piperylene.

If Friedel-Crafts catalysts are used, medium dihalides with chlorine and / or bromine groups and a branched or unbranched carbon skeleton of 5 to 13 carbon

The elimination of water in the course of the reaction showed the presence of 1-tolyl-1-oxyundecene on, which is produced by elimination of water in tolylundecadiene passed over. The properties of fractions 1 and 2 corresponded to a mixture of isomers Tolyl-undecenes and tolyl-undecadienes. the The properties of fraction 3 corresponded to a mixture of the various isomeric di-tolyl-undecenes. The residue contained some tri-tolyl-undecene.

(b) Mixtures of the isomeric di- (methylcyclohexyl) -undecanes

The hydrogenation of the combined fractions 1 and 3 according to the procedure of Example I gave a very high-energy fuel which contained the various isomers di- (methylcyclohexyl) -undecane and had a combustion energy of more than 8.988 kcal / l (net).
Example XXIX

(a) Mixtures of l, 10-di (tolyl) decanes

552 g of toluene (6 mol) and 40 g of freshly sublimed aluminum chloride (0.3 mol) were added to a glass vessel with a capacity of 11, equipped with a reflux condenser, stirrer and thermometer, which was kept at 90 ° C. in a water bath. 150 g (0.5 mol) of decamethylene dibromide-1.10 (refractive index nf = 1.4940) were added dropwise over the course of 3 hours, the temperature being 85 ° C. for the first 2 hours and 93 ° C. for the third hour ° C. The mixture was then stirred at a temperature of about 90 ° C. for a further 2.5 hours. The reaction mixture was poured onto 650 g of ice to which 65 ml of 37% strength hydrochloric acid had been added. The hydrocarbon layer was separated, washed with 300 ml of 6.2% aqueous hydrochloric acid and dried with a sodium chloride column.

fraction Bp ° C / mm Hg n% ³ yield
G 1
2
3
4th
5
6th
7th 83 to 114/747
114 to 120/747
40 to 93/2 to 3
93 to 136/1 to 2
136 to 172/1 to 2
172 to 240/2 to 4
Dark oil residue 1.4944
1.4924
1.5020
1.5096
1.5225
1.5550 400 ml
50 g
28 g
26.5 g
53 g
18 g
9g

Fraction 5 had a density Df = 0.903 and fraction 6 a density Df = 0.950. These fractions contained the l, 10-di- (tolyl) -decane in a mixture with smaller amounts of tolyldecane and isomeric di- (10-tolyldecyl) -toluenes.

(b) Mixtures of the l, 10-di (methylcyclohexyl) decanes

A high pressure autoclave was charged with 20 g of the combined fractions 5 and 6, 80 g of cyclohexane and 4.6 g of Raney nickel (Girdler-49-A) and filled ^{with hydrogen at a pressure of 70 kg / cm 2.} The mixture was heated to 150 ° C. and shaken until the hydrogenation was complete. After filtering off the catalyst, the cyclohexane was removed by distillation. A mixture of the isomeric l, 10-di- (methyl-cyclohexyl) -decanes in a mixture with smaller amounts of methylcyclohexyldecane and di- (10-methyl-cyclohexyldecy ^ -methylcyclohexane isomers) was obtained in almost quantitative yield. 988 kcal / 1 (net).

The mixtures of the isomeric di (alkylcyclohexyl) alkanes illustrated by Formula I are used as such used as very high energy fuels. If necessary, they can also be mixed with smaller ones Quantities of other high energy hydrocarbon fuels and other fuels used will. So the fuels according to the invention z. B. in amounts of at least 25% or more can be used to improve the fuel efficiency of fuels known per se such as kerosene, dialkylcyclohexane, Cumene, hydrogenated cumene, dieumene, hydrogenated dieumene, paramenthane and the like. They can also be used together with other fuels, such as borohydride, decaborane, and alkylborohydrides Trialkylboranes and the like can be used to reduce their flammability and toxicity.

It has been found that when the number of carbon atoms of the alkyl groups is increased above the for the use as liquid rocket fuel favorable range from 14 to 30 carbon atoms as well For fuel purposes in question substances of high energy content can be obtained. These substances represent liquids of high viscosity or solids that are suitable for use as easily mobile Liquids must be heated or melted for combustion.

These saturated compounds, including their partially hydrogenated starting materials, can also for fuel purposes can also be used for the other purposes indicated above.

In summary, it can therefore be stated that the substances of the various formulas I to III, where R ¹ and R ^{2 are} alkyl radicals with 1 to 13 carbon atoms, Y is an alkylene bridge with 1 to 13 carbon atoms, m is an integer from 1 to 3, η is an integer from 1 to 4, in which the total number of carbon atoms is above the range of up to 30 carbon atoms and preferably in the range of 30 to 54 carbon atoms, are valuable fuels, while the higher hydrogenated compounds are also suitable for fuel and other purposes. The partially hydrogenated and non-hydrogenated compounds of the formulas IV to VE and VIII and IX which occur as intermediate stages represent precursors for the production of the fuels obtained by hydrogenation. can be used in liquid form. In addition, they are suitable as lubricants, heat transfer media, hydraulic fluids and as plasticizers for elastomers and plastomers, adhesives and other film-forming or plastically deformable compounds.

The higher homologues and their isomers are named after those used to make the hydrogenated fuels and their intermediates obtained processes used, but with more or less molar proportions of the various reaction components are used.

Claims (7)

Patent claims: 1. Liquid or liquid-viscous to solid fuel for liquid or solid rocket and / or Jet fuels, characterized in that that the fuel is an isomer mixture of liquid, liquid-viscous to solid di- (alkylcyclohexyl) alkanes or (alkylcyclohexyl) - (cyclohexyl) alkanes of the general formula H-YH-EN- (R *) ,, ^ where R ¹ and R ^{2 are} unbranched or branched, lower alkyl radicals having 1 to 13, preferably 1 to 5 carbon atoms, Y is an alkylene or alkylidene radical serving as a bridge with 1 to 13 carbon atoms, m is an integer from 1 to 3, η is an integer Number from 1 to 4 and mean a saturated benzene nucleus is that the mixture has a density above 0.8 and a Heat of combustion of over 8.323 kcal / 1, and that the basic number of carbon atoms in the molecule in the case of liquid fuel fourteen to thirty and in the case of liquid viscous to solid fuels thirty to forty-one amounts to. 2. Fuel according to claim 1, characterized in that R ¹ and / or R ² and / or Y have 1 to 4 carbon atoms and are preferably methyl or methylene radicals. 3. Fuel according to claim 1 and 2, characterized in that R ¹ and / or R ² and / or Y are alkyl or alkylene radicals with branched carbon chains. 4. Fuel according to claim 1 to 3, characterized in that the cyclohexyl radicals in each case are connected to two terminal alkyl radicals. 5. Fuel according to claim 1 to 4, characterized in that the isomer mixture additive another isomer mixture of the formula (R ¹ ) »f H-; and or -H-j-Y H-I-Y \ X 20th in which R ¹ , R ² , Y, m and η have the same meaning as in claim 1 and ρ is the number 2 or 3, contains. 6. Fuel according to claim 1 to 4, characterized in that the isomer mixture additionally nor a content of compounds of the formula H-Y - H and / or H-Y H- v-x where Y has the same meaning as in claim 1 and ρ is 2 or 3. 7. Fuel according to claim 1 to 6, characterized in that the one or more isomer mixtures additionally contains a fuel known per se, such as borohydrides or hydrocarbons. Considered publications:
U.S. Patent No. 2,662,110;
I am. Chem. Soc, Vol. 76, 1954, pp. 5108-5115. 409 707/111 10.64 © Bundesdruckerei Berlin